PT932643E - MASSES OF IGNIFUGAS MOLDING - Google Patents

Abstract

Thermoplastic molding compositions compriseA) from 30 to 96% by weight of a polyesterB) from 1 to 30% by weight of melamine cyanurateC) from 1 to 30% by weight of at least one phosphorus-containing flame retardantD) from 0.01 to 5% by weight of at least one ester or amide derived from a saturated or unsaturated aliphatic carboxylic acid having from 10 to 40 carbon atoms and a saturated aliphatic alcohol or &mine having from 2 to 40 carbon atomsE) from 0 to 60% by weight of other additives and processing aidswhere the total of the percentages by weight of components A) to E) is 100%.

Description

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The invention relates to thermoplastic molding compositions containing A) 30 to 96% by weight of a polyester, B) 30% by weight of melamine cyanurate, C) 30% by weight of the polyesters. less a phosphorus-containing fire retardant, D) 0.01 to 5% by weight at least one saturated or unsaturated aliphatic carboxylic acid ester or amide having 10 to 40 C atoms, with saturated aliphatic alcohols or amines having from 2 to 40 C atoms, E) 0 to 60% by weight other additives and processing aids, wherein the sum of the weight percentages of components A) to E) is equal to 100%. The invention further relates to the use of the molding compositions according to the invention for the preparation of fibers, sheets and shaped bodies, as well as any type of molded body obtainable therewith.

There is a growing commercial interest in halogen-free flame retardant polyesters. Essential requirements at the level of the flame retardant are: clear own color, sufficient thermal stability for incorporation into thermoplastics, as well as its effectiveness in reinforced and non-reinforced polymers (so-called Docht effect on

In addition, the combustion test shall be approved in accordance with UL 94 with V-O.

In addition to halogen-containing systems, four halogen-free FR systems are in principle used in thermoplasts: inorganic flame retardants, which have to be inserted in high amounts to show efficacy. - nitrogen-containing FR systems, such as melamine cyanurate, which has limited effectiveness in thermoplastics, for example polyamide. In reinforced polyamide it is only effective in conjunction with shortened glass fibers. In polyethers, melamine cyanurate is not effective. phosphorus-containing FR systems, which are generally not effective on polyesters. phosphorus / nitrogen-containing FR systems such as ammonium polyphosphate or melamine phosphates, which do not have sufficient thermal stability for thermoplastics which are processed at temperatures above 200 ° C.

From JP-A 03 / 281,652, alkylene polyterephthalates are known, which contain melamine cyanurate and glass fibers, as well as a phosphorus-containing flame retardant. These molding compounds contain phosphoric acid derivatives, such as phosphoric acid esters (valence state +5), which tend to " flower " thermal overload.

These drawbacks are also shown for the combination of melamine cyanurate with resorcinol bis- (diphenylphosphate), which is known from JP-A 05/070671. The present invention has therefore aimed to provide molding compounds of inhomogeneous polyesters, which meet the V-0 rating according to UL 94 and pass the incandescent filament test. With this, the deposit in the mold should be minimized, therefore, a so-called flourishing of the flame retardant should be as hindered as possible. In addition, the mechanical properties should be widely maintained.

In this context, the thermoplastic molding masses defined at the beginning were found. Preferred embodiments may be derived from the claims.

As component (A), the molding compositions according to the invention contain 30 to 96, preferably 40 to 93 and in particular 50 to 85% by weight of a thermoplastic polyester.

Generally, the polyesters are used based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxylated compound.

A first group of preferred polyesters are the alkylene polyterephthalates having 2 to 10 carbon atoms in the part corresponding to the alcohol.

Such alkylene polyterephthalates are themselves known and are described in the literature. They contain an aromatic ring in the main chain, originating from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, for example, by halogen, such as chlorine and bromine, or by C1 -C4 -alkyl groups, such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups .

These alkylene polyterephthalates may be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxylated compounds.

Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids may be substituted with aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecane diacids and cyclohexanedicarboxylic acids. 4 saMJ »

Of the dihydric aliphatic compounds, diols having 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,4-buyanediol, 1,6-hexanudiol, 1,4-hexanediol, 1,4- hexanedio], 1,4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.

Especially preferred polyesters (A) are alkylene polyterephthalates, which are derived from alkanediols having from 2 to 6 C. Particularly preferred are polyethylene terephthalate and butylene polyterephthalate or mixtures thereof. The viscosity index of the polyester (A) is generally in the range of 70 to 220, preferably 80 to 160 (determined in a 0.5% by weight solution of a phenol / o-dichlorobenzene mixture 1: 1 at 25 ° C)).

Especially preferred are polyesters, the terminal carboxyl groups content of up to 100 mval / kg, preferably up to 50 mval / kg and in particular up to 40 mval / kg of polyester. Polyesters of this type may, for example, be prepared according to the process of DE-A 44 01 055. The content in terminal carboxyl groups is generally determined by titration processes (for example potentiometry).

Especially preferred molding compounds contain as component (A) a blend of polyethylene terephthalate (PET) and polyethylene terephthalate (PBT). The proportion of polyethylene terephthalate in the mixture is preferably up to 50, especially 10 to 30% by weight, relative to 100% by weight of A).

Molding masses of this type according to the invention have very good flame retardant properties and better mechanical properties.

In addition, it is advantageous to introduce PET recyclates (also referred to as PET fragments) in admixture with alkylene polyterephthalates, such as PBT.

In general, recycling means: 5 5

1) the so-called post-industrial recycled materials: these are production wastes occurring during polycondensation or during processing, for example, spindles during injection molding processing, initial injection molding processing materials or extrusions or cut edges of sheets or sheets extruded. 2) post-consumer recycled: these are plastic articles, which after use are collected and prepared by the final consumer. Articles of far dominance, taking into account their quantity, are PET bottles formed by means of blowing, for mineral water, soft drinks and juices.

Both recycled types can exist either as ground material or in the form of granulates. In the latter case, the raw recycles are, after separation and purification, melted in an extruder and pellets. By this means, handling, irrigation and dosing capacity for further processing steps are, in most cases, simplified.

Both the granules and the ground materials of the existing recycles can be used, the maximum chain length being 6 mm, preferably less than 5 mm.

Due to the hydrolytic separation of polyesters during processing (through traces of moisture) the need to pre-dry the recycling was imposed. The residual moisture content after drying is preferably from 0.01 to 0.7, in particular from 0.2 to 0.6%.

As other groups are to name fully aromatic polyesters, which are derived from aromatic dicarboxylic acids and aromatic dihydroxylated compounds.

As aromatic dicarboxylic acids, the compounds already described for the alkylene polyterephthalates are suitable. Preferably used are mixtures of from 5 to 100 mol% of isophthalic acid and 0 to 95 mol% of terephthalic acid, especially mixtures of about 80% terephthalic acid with 20% isophthalic acid to an approximately equivalent mixture of these two acids.

The aromatic dihydroxylated compounds preferably have general formula I

OH in which Z represents an alkylene or cycloalkylene group of up to 8 carbon atoms, an arylene group of up to 12 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in which m has the value of 0 to 2. The compounds I may also have on the phenyl groups C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents.

Examples of the starting elements of these compounds are dihydroxydiphenyl, di (hydroxyphenyl) alkane, di (hydroxyphenyl) cycloalkane, di (hydroxyphenyl) sulphide, di (hydroxyphenyl) ether, hydroxyphenyl) ketone, di- (hydroxyphenyl) sulfoxide, a, ar-di- (hydroxylphenyl) -dialkylbenzene, di- (hydroxyferro) sufono, di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone, as well as their alkyl or halogenated nucleus.

Of these, 4,4'-dihydroxydiphenyl, 2,4-di- (4'-hydroxyphenyl) -2-methylbutane, α, α'-di- (4-hydroxyphenyl) -β-diisopropylbenzene, 2,2- di- (3'-methyl-4'-hydroxyphenyl) propane and 2,2-di- (3'-chloro-4'-hydroxyphenyl) propane, in particular 2,2-di- (4'-hydroxyphenyl) propane, 2,2- di- (3 ', 5-dichlorodihydroxyphenyl) propane, 1,1-di- (4'-hydroxyphenyl) cyclohexane, 3,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfono and 2,2- di- (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane or mixtures thereof.

Naturally, mixtures of alkylene polyterephthalates and fully aromatic polyesters can also be introduced. These generally contain 20-98% by weight of the alkylene polyterephthalate and 2 to 80% by weight of the fully aromatic polyester.

Polycarbonates, which can be obtained by the polymerization of aromatic dihydroxylated compounds, in particular bis- (4-hydroxyphenyl) -2,2-propane (bisphenol A) or their derivatives, are also to be understood in the context of the present invention. derivatives, for example with phosphorus. Corresponding products are themselves known and described in the literature, much of which is also obtainable on the market. The amount in polycarbonates is up to 90% by weight, preferably up to 50% by weight, relative to the 100% by weight of component (A).

Of course, block copolymers of polyesters, such as copolyether esters, can also be used. Such products are themselves known and described in the literature, for example in US-A 3 651 014. Corresponding products, for example Elytrel (DuPont), are also obtainable on the market.

As component B), the thermoplastic molding compositions according to the invention contain 1 to 30, preferably 1 to 20, and in particular 5 to 20% by weight of melamine cyanurate as a flame retardant. The melamine cyanurate (component B) used according to the invention is a reaction product of preferably equimolar amounts of melamine (formula I) and cyanuric acid or isocyanuric acid (formulas IIa and IIb). nh2 (I) h2n

N-C (O)

N NH2 OH | 0 I! N <C <N < HNâ,,CNH + 1 &gt; (IIb) enol form keto

It is obtained, for example, by reaction of aqueous solutions of the starting compounds at 90 to 100 ° C. The commercially available product is a white powder having a mean grain size dso of 1.5-7 μιη.

Suitable flame retardants C) are present in the molding compositions according to the invention in amounts of from 1 to 30, preferably from 1 to 25, and in particular from 10 to 20% by weight, based on the total weight of components A) to E).

In the case of component C), these are compounds containing organic and inorganic phosphorus, in which phosphorus has a valence state of -3 to +5. By valence state the concept of &quot; oxidation state &quot; as it is presented in &quot; Lehrbuch der Anorganischen Chemie &quot; of A.F. Hollemann and E. Wiberg, Walter des Gruyter and Co. (1964, pp. 57-70), pages 166 to 177. Phosphorus compounds with a valence state of -3 to +5 are derived from phosphine (-3), diphosphine (-2), 9 phosphinoxide (-1), elemental phosphorus (+0), hypophosphorous acid (+1), phosphorous acid (+3), hypodiphosphoric acid (+4) and phosphoric acid (+5).

Only a few examples are mentioned of the high number of phosphorus-containing compounds.

Examples for phosphine-containing compounds of the phosphine class, which have a valence -3 state, are aromatic phosphines, such as triphenylphosphine, tritolylphosphine, trionylphosphine, trinaphthylphosphine, among others. Especially suitable is triphenylphosphine.

Examples of phosphorus compounds of the diphosphine class, which have a valence -2 state, are tetraphenyldiphosphine, tetranaphthyldiphosph, among others. Especially suitable is tetranaphthyldiphosph.

Compound compounds of valence state -1 are derived from the phosphinoxide.

Suitable are phosphinoxides of the formula I wherein R 1, R 2 and R 3, which may be the same or different, mean alkyl, aryl, alkylaryl, or cycloalkyl groups having 8 to 40 carbon atoms.

Examples for phosphoxides are triphenylphosphinoxide, tritolylphosphinoxide, trisnonylphenylphosphinoxide, tricyclohexylphosphinoxide, tris- (n-butyl) -phosphinoxide, tris- (n-hexyl) -phosphinoxide, tris- (n-octyl) -phosphinoxide, tris- (cyanoethyl) - phosphoxide, benzylbis- (cyclohexyl) phosphinoxide, benzylbisphenylphosphinoxide, phenylbis- (n-hexyl) -phosphinoxide. Especially preferred is triphenylphosphinoxide, tricyclohexylphosphinoxide and tris- (n-octyl) phosphinoxide.

Also suitable is triphenylphosphine sulphide and the derivatives of the above-described phosphoxides.

The valence state phosphorus Γ0 corresponds to the elemental phosphorus. Of note is the red match and the black match. Preferred is the red phosphorus

Phosphorus compounds with &quot; oxidation state &quot; +1 are, for example, hypophosphites. They may have a saline character or may be purely organic in nature. Examples are calcium hypophosphite and magnesium hypophosphite, in addition to these there are also double hypophosphites or complex hypophosphites, or organic hypophosphites, such as esters of cellulose hypophosphites, esters of hypophosphorous acids with diols such as 1,10-dodecyldiol. Phosphinic acids and their anhydrides, for example diphenylphosphinic acid, may also be used. Further relevant are di-p-tolylphosphinic acid, dicresylphosphinic anhydride. Also useful are compounds such as hydroquinono-bis (diphenylphosphinic), ethylene glycol-bis (diphenylphosphinic), propylene glycol-bis (diphenylphosphinic) ester, among others. Also suitable are aryl (alkyl) phosphinamides, such as diphenylphosphinic acid dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid derivatives, for example p-tolylsulfonamidodiphenylphosphinic acid. Preferably used are hydroquinone bis (diphenylphosphoric acid) ester and ethylene glycol bis (diphenylphosphinic) acid ester and hydroquinone bisphenylphosphate.

Phosphorus compounds of oxidation state +3 are derived from phosphorous acid. Suitable are cyclic phosphonates, which are derived from pentaerythritol, neopentyl glycol or catechol. In addition, phosphorus in the +3 valence state is contained in triaryl (alkyl) phosphites, such as, for example, triphenylphosphite, tris (4-decylphenyl) phosphite, tris (2,4-di-trans-butylphenyl) phosphite or phenyldecylphosphite , among others. However, diphosphites such as 1,2-bis (diphosphite) of propylene glycol or cyclic phosphites derived from pentaerythritol, neopentyl glycol or catechol are also of interest.

Especially preferred are methylene-pentyl glycol phosphonate and methylene-pentyl glycol phosphite, as well as diphosphonate and dimethylpentaerythritol phosphite.

As phosphorus compounds with a +4 oxidation state, the hypodiphosphates, such as tetraphenyl hypodiphosphate or bisneopentyl hypodiphosphate, are especially relevant.

Phosphorus compounds with a +5 oxidation state are particularly concerned with alkyl and aryl-substituted phosphates. Examples are phenylbisdodecyl phosphate, phenylethyl hydrogen phosphate, phenyl bis (3,5,5-trimethylhexyl) phosphate, ethyl diphenylphosphate, 2-ethylhexyl di (tolyl) phosphate, diphenyl hydrogenphosphate, p-tolyphosphate of bis (2-ethylhexyl) phenylphosphate, di (nonyl) phenylphosphate, phenylmethyl hydrogenphosphate, di (dodecyl) p-tolylphosphate, p-tolyl-bis (2-ethylhexyl) phosphate - (2,5,5-trimethylhexyl) or 2-ethylhexyl diphenylphosphate. Especially suitable are phosphorus compounds, in which each radical is an aryloxy radical. Very particularly suitable is resorcinol triphenylphosphate and bis- (diphenylphosphate) and its substituted nucleoside derivatives of the general formula OR5 OR6-

r4 -or-P-r8-P

II 0

In which the substituents have the following meaning: R 4 -R 7 is an aromatic radical having 6 to 20 carbon atoms, preferably a phenyl radical, which may be substituted with alkyl groups having 1 to 4 carbon atoms, preferably methyl , a divalent phenol, preferably

-O

0- or

and n = 1 to 100, preferably 1 to 5.

In addition, cyclic phosphates may also be used. Particularly suitable are, therefore, diphenylpenellerildehyde diphosphate and feuilueopentyl phosphate.

In addition to the aforementioned lower molecular phosphorus compounds, oligomers and polymers of phosphorus compounds are also of interest.

Such non-halogenated organic phosphorus polymers with phosphorus in the polymer chain arise, for example, during the preparation of pentacyclic unsaturated phosphine dihalides, for example as described in DE-A 20 36 173. The molecular weight of polyoxides, as determined by vapor pressure osmometry in dimethylformamide, should be in the range of 500 to 7,000, preferably in the range of 700 to 2,000. Phosphorus therefore has an oxidation state of -1.

In addition, inorganic coordination polymers of aryl (alkyl) -phosphinic acids, such as, for example, poly-p-sodium (I) -methylphenyl phosphinate may be used. Its preparation is described in DE-A 31 40 520. The phosphorus has an oxidation index of +1.

Such halogen-free polymer phosphorus compounds may also be produced by the reaction of a phosphonic acid chloride such as phenyl-, methyl-, propyl-, styryl- and vinylphosphonic acid dichloride with bifunctional phenols such as hydroquinone, resorcinol, 2,3,5-trimethylhydroquinone, bisphenol-A, tetramethylbisphenol-A.

Other halogen-free polymer phosphorus compounds which can be inserted into the molding compositions according to the invention are prepared by reacting phosphorus oxide trichloride or phosphoric acid ester dichlorides with a mixture of mono-, bi- and trifunctional compounds and other compounds with hydroxyl groups (see Houben-Weyl-Muller, Thieme-Verlag Stuttgart, &quot; Organische Phosphorverbindungen &quot; Part II (1963). Polyphosphoric esters can also be prepared by re-esterification reactions of phosphonic acid esters with bifunctional phenols (see DE-A 29 25 208) or by reactions of phosphonic acid esters with diamines or diamides or hydrazides (see US Pat. No. 4,403,075) . Also relevant is inorganic ammonium polyphosphate.

According to EP-B 8 486, oligomeric pentaseritrite phosphites, phosphates and phosphonoes can also be used, for example Mobil Antiblaze® 19 (registered trademark of Mobil Oil).

As component D), the molding compositions according to the invention contain 0.01 to 5, preferably 0.05 to 3 and in particular 0.1 to 2% by weight of at least one ester or amide of an acid saturated or unsaturated aliphatic carboxylic acid having from 10 to 40, preferably 16 to 22 C atoms, with saturated aliphatic alcohols or with amines having 2 to 40, preferably 2 to 6, C atoms.

The carboxylic acids may be mono or di-valent. Pelargonic acid, palmitic acid, lauric acid, margalic acid, dodecanic diacid, behenic acid and in particular stearic acid, capric acid, as well as montanic acid (mixtures of fatty acids with 30 to 40 C atoms) .

The aliphatic alcohols may be mono to tetravalent. Examples for alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, wherein glycerin and pentaerythritol are preferred.

The aliphatic amines may be mono to trivalent. Examples for such are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, wherein ethylenediamine and hexamethylenediamine are especially preferred. Preferred esters or amides are respectively glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerine monobehenate and pentaerythritoltetrateate.

Mixtures of different esters or amides or esters in combination with amides may also be used, wherein the ratio of the mixture may be any. A \ ./- 14

As component E), the molding compositions according to the invention may contain 0 to 60, in particular up to 50% by weight of a common additive and a processing aid.

Common Additives E) are for example in amounts up to 40, preferably up to 30% by weight of copolymers with elasticity of cautchu (often also referred to as impact resistance modifiers, elastomers or cautchus).

Generally, these are copolymerizates which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutadiene, isopropene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylate or methacrylate having 1 to 18 carbon atoms in the component alcohol.

Polymers of this type are, for example, described in Houben-Weyl, &quot; Methoden der organischen Chemie, Vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, 1961), pages 392-406 and in the monograph by CB Bucknall, &quot; Toughened Plastics &quot; (Applied Science Publishers, London, 1977).

In the following, some of the preferred types of such elastomers are shown.

Preferred types of such elastomers are so-called ethylene-propylene (EPM) casks or ethylene-propylene-diene (ESP) casings.

The cautchus-EPMs generally have virtually no double bonds, whereas the cautchus-EPDMs may have 1 to 20 double bonds / 100 C-atoms.

As diene monomers for cautchus-EPDM are, for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms, such as penta-1,4-diene, hexa-1,4-diene, hexa-1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes, such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, as well as alkenylnorbornenes 2-norbornene, 5-butylidene-2-norbomene, 2-methallyl-5-norbomene, 2-isopropenyl-5-norbornene and tricyclodienes, such as 3-methyl-tricyclo (5.2.1.0.2.6) - 3,8-decadiene or mixtures thereof. Preferred are hexa-1,5-diene, 5-ethylindenonorbornene and dicyclopentadiene. The diene content of the EPDM-cautchus is preferably 0.5 to 50, in particular 1 to 8% by weight, based on the total weight of the cautchu.

Cautchus-EPM or cautchus-EPDM may preferably also be grafted with reactive carboxylic acids or derivatives thereof. There are, for example, acrylic acid, methacrylic acid and its derivatives, for example glycidyl (meth) acrylate, as well as maleic anhydride.

Another preferred group of cocoa is copolymers of ethylene with acrylic and / or methacrylic acid and / or the esters of these acids. In addition, the cautchus may further contain dicarboxylic acids, such as maleic acid and fumaric acid or derivatives thereof, for example, esters and anhydrides, and / or epoxy group containing monomers. These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably introduced into the cup by adding to the monomeric mixture monomers containing dicarboxylic acid groups or epoxy groups of general formula I or II or III or IV40 (000) = 0 (000) 4 (I)

cc (II) with

O

(III): wherein R 1 to R 9 represents hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, integer from 0 to 10 and an integer from 0 to 5.

Preferably, the radicals R 1 to R 9 are hydrogen, wherein m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allylglycidyl ether and vinylglycidyl ether.

Preferred compounds of formula I, II and IV are maleic acid, maleic anhydride and esters of acrylic and / or methacrylic acid containing epoxy groups, such as glycidyl acrylate, glycidyl methacrylate and esters with tertiary alcohols, such as t-butyl acrylate. The latter, although they do not have free carboxyl groups, their behavior is close to that of the free acids and are therefore termed latent carboxylic monomers.

The copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing anhydride groups, as well as the remaining amount in esters of methacrylic acid.

Especially preferred are copolymerizates of 50 to 98, in particular 55 to 95% by weight of ethylene, 0.1 to 40, in particular 0.3 to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, ) acrylic acid and / or maleic anhydride, and 1 to 45, in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.

Other preferred esters of acrylic and / or methacrylic acid are esters of methyl, ethyl esters, propyl esters and i- or t-butyl esters.

In addition, vinyl esters and vinyl ether esters may also be included as comonomers.

The ethylene copolymers described above may be prepared by processes known per se, preferably by statistical copolymerization under high pressure and elevated temperature. The corresponding procedures are generally known.

Preferred elastomers are also emulsion polymerizates, the preparation of which is, for example, described by Blackley in the monograph &quot; Emulsion Polymerization &quot;. Usable emulsifiers and catalysts are known per se.

In principle, homogeneously formed elastomers or also those with a capsule formation are used. The capsule type synthesis is determined by the order of addition of each of the monomers; also the morphology of the polymers is influenced by this order of addition.

Only monomer representatives for the preparation of the olefin component of the elastomeric acrylates, such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene, as well as mixtures thereof, are currently named. These monomers may be copolymerized with other monomers such as styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate. The plastic phase or the elastomer phase of the elastomers (having a glass transition temperature of less than 0 ° C) may constitute the core, the outer shell or an intermediate shell (in elastomers with a synthesis greater than two capsules); in multi-capsule elastomers may also result in several capsules of a cautchu phase.

If, in addition to the carbon phase, one or more hard components (with a glass transition temperature of more than 20 ° C) are present in the synthesis of the elastomers, then these are generally prepared by styrene polymerization. Acrylonitrile, α-methylstyrene, p-methylstyrene, acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the primary monomers. In addition, small amounts of other comonomers may also be introduced here.

In some cases, it has proved advantageous to insert emulsion polymerizates, which have surface reactive groups. Such groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups, as well as functional groups which may be introduced by the use of monomers of the general formula R10 R11 CH =

Wherein the substituents may have the following meaning; R10 is hydrogen or a C1 to C4 alkyl group, R11 is hydrogen, a C1 to C6 alkyl group or an aryl group, in particular phenyl, R12 is hydrogen, a C1 to C10 alkyl group, a C1-6 alkyl group, C 1 -C 12 -aryl or -OR 13, R 13 a C 1 to C 6 -alkyl group or a C 3- to C 12 -aryl group, which may optionally be substituted with O or N containing groups, X a chemical bond, alkylene or Ce-Cu-arylene or

O

II

Or a C1 to C10 alkylene or C6 to C12-arylene group. - 19

Also the graft monomers described in EP-A 208 187 are suitable for the introduction of surface reactive groups.

Further examples are acrylamide, methacrylamide and substituted esters of acrylic or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-diethylamino) ethyl acrylate.

In addition, the particles of the cocoa phase may also be cross-linked. As monomers with crosslinking action are examples, buta-1,3-diene, divinylbenzene, diallylphthalate and dihydrodicyclopentadienyl acrylate, as well as the compounds described in EP-A 50 265.

The so-called crosslinking graft monomers ("graftlinking monomers"), therefore monomers with two or more polymerizable double bonds, which during polymerization may react at different rates may also be used. Preferably, those compounds are used in which at least one reactive group polymerizes at approximately the same rate as the remaining monomers, while the other reactive group (or reactive groups) polymerizes (polymerizes), for example, much more slowly. The different polymerization rates give rise to a certain amount of unsaturated double bonds in the cocoa. If another phase is subsequently grafted on such a caudillo, then the double bonds in the cautchu react, at least in part, with the graft monomers, by the formation of chemical bonds, whereby the grafted phase is at least partially , bonded to the graft base through chemical bonds.

Examples for such crosslinking graft monomers are allyl-containing monomers, in particular allyl esters of unsaturated ethylenic carboxylic acids, such as allyl acyl, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. 20

In addition to these, there are many other suitable crosslinking graft monomers; for further details refer to, for example, US-PS 4 148 846.

In general, the participation of these crosslinking monomers in the impact modifier polymer comprises up to 5% by weight, preferably not more than 3% by weight, relative to the impact modifier polymer.

Next, there are some preferred emulsion polymerizates. In the first instance, they are at present to refer to graft polymerizates with a core and at least one outer capsule, which have the following formation:

Type Monomers for the core Monomers for the envelope I Buta-1,3-diene, isoprene, n-butyl acrylate, ethylhexyl acrylate or mixtures thereof Styrene, acrylonitrile, methyl methacrylate II As by but using crosslinkers N-Butyl acrylate, ethyl acrylate, methyl acrylate, buta-1,3-diene, isoprene, ethylhexyl acrylate. As I or II, as in I or II, but using monomers with reactive groups as described in the present V Styrene, acrylonitrile, methyl methacrylate or mixtures thereof First monomer casing as described for the core in I and II, second casing as described for the I or IV casing.

These graft polymerizates, in particular ABS-polymer and / or ASA in amounts up to 40% by weight, are preferably used for the modification of the impact strength of PBT, optionally in admixture with up to 40% by weight of polyethylene terephthalate. Mixing products are obtainable under the trademark Ultradur®S (formerly Ultrablend®S from BASF AG). ABS / ASA blends with polycarbonates are obtainable on the market under the tradename Terblend® (BASF AG).

Instead of graft polymerizates having a pluricapsular formation, homogeneous, and therefore monocapsular, elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or copolymers thereof may also be inserted. Also these products may be prepared by the use of crosslinking monomers or reactive group monomers.

Examples for preferred emulsion polymerizates are copolymers of n-butyl acrylate / (meth) acrylic acid, copolymers of n-butyl acrylate / glycidyl acrylate or copolymers of n-butyl acrylate / glycidyl methacrylate, graft polymerizates with a inner core of n-bullet acrylate or based on butadiene and an outer shell of the aforementioned copolymers and copolymers of ethylene with comonomers, which give rise to reactive groups.

The elastomers described may also be prepared by other customary methods, for example by suspension polymerization.

Silicone casings such as those described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290 are likewise preferred.

Naturally, mixtures of the types of cautchus previously shown may also be inserted.

As fillers in the form of fibers or particles, carbon fibers, glass fibers, glass beads, amorphous silicic acid, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, grease, quartz powder, mica, barium sulphate and feldspar, which are inserted in amounts up to 50% by weight, in particular up to 40% by weight.

Preferred fiber fillers are carbon fibers, aramid fibers and potassium titanate fibers, the glass fibers being especially preferred as E-glass. These may be inserted into molds commonly marketed as wicks or cut glasses.

Fiber-like fillers may be superficially pretreated with a silane compound, to improve compatibility with thermoplastics. III Ϊ • ta ··

I

Suitable silane compounds are those of the general formula III (X- (CH 2) n) k-Si- (O-CmH 2m + 1) 2-k in which the substituents have the following meaning: X NH 2 -, CH 2 -CH 2 - , HO-, n is an integer of 2 to 10, preferably 3 to 4, m is an integer of 1 to 5, preferably 1 to 2, and an integer of 1 to 3, preferably 1.

Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, as well as the corresponding silanes, which as the X substituent have a glycidyl group.

The silane compounds are generally inserted in amounts of from 0.05 to 5, preferably from 0.5 to 1.5, and in particular from 0.8 to 1% by weight (relative to D), for surface coverage .

Suitable are also acicular mineral fillers.

In the context of the invention, acicular mineral charges are understood to mean a mineral filler having a strongly creased acicular character. As an example, acicular volastinitis is referred to. Preferably, the mineral has a C / D ratio (diameter length) of 8: 1 to 35: 1, preferably from 8: 1 to 11: 1. The mineral filler may optionally be pretreated with the silane compounds previously mentioned; pre-treatment is not, however, absolutely necessary.

Other fillers are kaolin, calcined kaolin, wollastonite, talc and grease. 23

As component E), the thermoplastic molding compositions according to the invention may contain customary processing aids, such as stabilizers, anti-oxidants, thermo-decomposition and ultraviolet light decomposition agents, glidants and demoulding agents, dyeing agents, such as dyes and pigments, germinating agents, plasticizers, etc.

As examples for anti-oxidants and thermostabilizers are phenols with stereo impediments and / or phosphites, hydroquinones, secondary aromatic amines, such as diphenylamine, various representatives of these substituted groups and their mixtures in concentrations up to 1% by weight, relative to the weight of the thermoplastic molding masses.

As UV stabilizers, which are normally used in amounts up to 2% by weight, relative to the molding mass, various substituted resorcinols, silicicates, benzotriazoles and benzophenones are to be mentioned.

As coloring agents, inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and soot may be added, in addition to organic pigments such as phthalocyanines, quinacridones, perylenes, as well as dyes such as nigrosine and anthraquinones.

Sodium phenylphosphate, aluminum oxide, silicon oxide, as well as, preferably talc, may be added as germinating agents.

Sliding and demoulding agents, which are usually added in amounts up to 1% by weight, are preferably long chain fatty acids (for example, stearic acid or behenic acid), their salts (for example, Ca or Zn stearate), and such as amide derivatives (for example ethylene bis-stearylamide) or montane waxes (mixtures of saturated, straight-chain carboxylic acids having a chain length of 28 to 32 C atoms), as well as lower molecular polyethylene or polypropylene waxes.

As examples for plasticizers are phthalic acid dioctyl ester, phthalic acid dibenzyl ester, phthalic acid bulylbenzyl ester, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.

The molding compositions according to the invention may further contain 0 to 2% by weight of fluorine-containing ethylene polymerizates. These are cetylcell polymers with a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight.

Examples for these are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with lower proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. These are, for example, described by Schildknecht in &quot; Vinyl and Related Polymers &quot;, Wiley-Verlag, 1952, pages 484 to 494 and by Wall in &quot; Fluorpolymers &quot; (Wiley Interscience, 1972).

These fluorine-containing ethylene polymerizates are homogeneously distributed in the molding pots and preferably have a particle size of 0 (average number value) in the range of 0.05 to 10 μm, especially 0.1 to 5 μm. These reduced particle sizes can be achieved, most preferably, by using aqueous dispersions of fluorine-containing ethylene polymerizates and their insertion into a polyester melt.

The thermoplastic molding compositions according to the invention may be prepared according to processes known per se, as the components are blended in standard mixing devices, such as spiral extruders, Brabender mills or Benbury mills, and subsequently extruded. After extrusion, the extrusion product can be cooled and fragmented. Individual components may also be premixed and then the remaining starting substances individually and / or optionally mixed. Mixing temperatures are generally between 230 and 290 ° C.

According to a preferred working method, components B) to D), as well as, optionally, the usual additives E) may be blended, confired and granulated with a polyester prepolymer. The granulate obtained is, in solid phase, subsequently, under inert gas, continuously or discontinuously, at a temperature below that of the melting point of component A), condensed to the desired viscosity.

The thermoplastic molding compositions according to the invention showed good mechanical properties and good flame retardant properties during the test of the glow filaments approved simultaneously. The processing takes place mostly without change of the polymer matrix and the deposit in the mold is greatly reduced. They are suitable for the preparation of fibers, sheets and shaped bodies, in particular, for application in the electrical and electronic area. These applications consist mainly of lamp parts, such as lamp holders and fastening devices for lamps, electrical plugs and sockets, coil body, capacitor boxes or contactors, as well as switches for safety fuses, relays and reflectors.

Examples 1 to 10 and examples of comparison 1 * to 6 *

Component A): polybutylene terephthalate having a viscosity index (VZ) of 130 ml / g and a terminal carboxyl group content of 34 mval / kg (Ultradur® B 4500 from BASF AG) (VZ measured in a solution of phenol / dichlorobenzene at 0.5% by weight), 1: 1 mixture at 25 ° C.

Component B: Melamine cyanurate

Component C: C1-triphenylphosphinoxide C2 triphenylphosphate C3 bis (diphenylphosphate) of resorcinol

Component D: pentaerythritoltetrateate

Component E: glass fiber cutting with a thickness of 10 μηι (epoxysilanized gums).

Components A) to E) were blended at 250 to 260øC in a twin-screw extruder and extruded in a water bath. After granulation and drying, test bodies were injected into an injection press and tested. The combustion test was performed according to UL 94 in 1/16 inch test bodies with the usual conditioning. The trend of migration in the bar was analyzed visually after storage, compared to an unstressed bar. The stability test at high operating temperatures was carried out as follows: molded parts (60x60x2 mm blades, about 11g) were injected. Each molded part was weighed on an analytical balance and heated to said temperature in an aluminum dish in a vacuum drying oven.

After the respective storage times (7 or 3 days) the samples cooled under vacuum were again weighed on an analytical balance and the weight loss determined. The composition of the molding masses and the results of the measurements can be taken from Tables 1 and 2.

Table 1

Example Composition in% by weight UL 94 1/16 " Migration for 7 days of storage 120 ° C 1 39.5A, 15B, 200, 0.5D 25E or not 1 * 40A, 15B, 200, 25E or 2 39, 5 A, 15B, 20C2, 0.5D 25E vo not 2 * 40A, 15B, 20C2.25E yes 3 39.5A, 15B, 20C3, 0.5D 25E or not 3 * 40A, 15B, 20C3 25E or yes *) For comparison

Table 2

Ex. 4 * 5 6 5 * 7 8 6 * 9 10 A 45.00 44.77 47.77 45.00 44.77 44.77 45.00 44.77 44.77 B 10.00 10.00 10 , 10.00 10.00 10.00 10.00 10.00 10.00 D - 0.23 0.53 - 0.23 0.53 - 0.23 0.53 Cl 15.00 15.00 15 , 00 C2 15.00 15.00 15.0 C3 15.00 15.00 15.00 E 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 Weight loss (%) after assembly 3d / 120 ° C 0.94 0.81 0.77 0.24 0.19 0.20 0.12 0.12 0.11 3d / 150 ° C 6.73 5, 71 5.23 4.06 2.21 0.35 0.33 0.28 0.17

Examples 11 to 23

Component Al: polybutylene terephthalate having a viscosity index (VZ) of 130 ml / g and a terminal carboxyl group content of 34 mval / kg (Ultradur® B 4500 from BASF AG) (VZ measured in a solution of phenol / o-dichlorobenzene to 0.5% by weight, 1: 1 mixture at 25 ° C).

Component A2a: Polyethylene terephthalate (PET) with a VZ of 76 ml / g.

Component A2b: recycled post-industrial PET in the form of cylindrical pellets. The viscosity index (ISO 1628-5, phenol / 1,2-dichlorobenzene 1/1) was 81 ml / g, the residual moisture after pre-drying was 0.02%

Component A2c: Polycarbonate with a VZ of 64 ml / g, measured in phenol / dichlorobenzene (1: 1) (Lexan® 161 from General Electric Plastics).

Component B: Melamine cyanurate

Component C / l: resorcinol bis (diphenylphosphate)

Component C / 2: calcium hypophosphite

Component D: pentaerythritoltetrateate

Component E: Cut glass fiber having a thickness of 10 pm (epoxysilonised gums).

Components A) to E) were mixed in a two-coil extruder, between 250 and 260 ° C and extruded in a water bath. After granulation and drying, test bodies were injected into an injection press and tested.

For the combustion test, bars were injected and tested according to the usual UL 94 conditions. The test of the incandescent filament occurred on 60/60 mm slides with a thickness of 1 and 3 mm. It was tested at the filament temperature of 960 ° C. The E-module was determined in accordance with DIN 527 as well as the burst voltage. The impact strength was measured according to ISO 179 / leU.

The results of the measurements and the composition of the molding masses can be taken from Table 3.

Table 3

Example 11 12 13 14 15 AI 49.7 39.7 39.7 39.7 29.7 A2a - 10 - - 20 A2b - - 10 - - A2c - - - 10 - B 10 10 10 10 10 C / l 10 10 10 10 10 D 0.3 0.3 0.3 0.3 0.3 E 30 30 30 30 30 E-module 6800 7800 7700 7800 8900 Tensile strength 84 91 90 103 109 Impact resistance 44 45 46 48 49 UL 94, 1.6 mm nc V2 V2 V2 V2 960 ° C 1/3 mm - / + + + + + + + + + + + + 29 Assay 16 12 18 19 120 21 AI 44.7 34.7 34.7 34.7 24.7 24.7 A2a - 10 - - 10 A2b - - 10 - - - A2c - - - 10 - - B 10 10 10 10 10 10 C / l D 0.3 0.3 0.3 0.3 0.3 0.3 E 30 30 30 30 30 30 E-module 6600 7700 7800 7900 6300 7200 Tensile strength (kJ / nr) 84 91 90 87 72 72 Impact resistance 44 45 46 57 35 33 UL 94 , 1.6 mm nc V2 V2 V2 V2 V0 960 ° C 1/3 mm +/- + + + + + + + + + + + + + + + + n.c .: not classified

Test 22 23 AI 49.7 29.7 A2a - 20 B 10 10 C / 2 10 10 D 0.3 0.3 E 30 30 E-module Tensile strength [MPA] 12200 12600 [kJ / m2] 113 118 UL 94 1.6 mm VI VI 960 ° C 1/3 mm ...... '/ Γ + / + Lisbon, 2QQ1 At

Dr. Américo da 5'ka Carvalho Agent O; Go to the next page. 210 ° C).

Claims (8)

A) 30 to 96% by weight of a polyester B) 1 to 30% by weight melamine cyanurate C) 1 to 30% by weight at least one flame retardant containing phosphorus D) 0.01 to 5% by weight at least one ester or amide of a saturated or unsaturated aliphatic carboxylic acid having 10 to 40 carbon atoms, saturated aliphatic alcohols or amines having 2 to 40 carbon atoms) 0 to 60% by weight other additives and processing auxiliaries, wherein the sum of the weight percentages of components A) to E) is equal to 100%. Thermoplastic molding compositions according to claim 1, containing as the flame retarding agent C) at least one phosphine oxide of the general formula I in which R 1, R 2 and R 3, which may be the same or different, represent alkyl, aryl, alkylaryl or cycloalkyl groups having 8 to 40 C atoms. Thermoplastic molding compounds according to claims 1 or 2, in which component C) is formed by triphenylphosphinoxide, triphenylphosphine, triphenylphosphate, resorcinol bis (diphenylphosphate) or triphenylphosphine or mixtures thereof. Thermoplastic molding compositions according to claims 1 to 3, containing 1 to 40% by weight of a fiber-like filler, as component E). Thermoplastic molding compositions according to claims 1 to 4, wherein component D) is pentaerythritoltetrateate. Thermoplastic molding compositions according to claims 1 to 5, wherein component A) consists of a mixture of polyethylene terephthalate and polybutylene terephthalate. Thermoplastic molding compositions according to claim 6, in which the share of polyethylene terephthalate in the blend is from 10 to 30% by weight. Thermoplastic molding compositions according to claims 6 or 7, in which the polyethylene terephthalate consists of a recycle having a residual moisture content of 0.01 to 0.7%. Use of the thermoplastic molding compositions according to claims 1 to 8 for the preparation of fibers, sheets and molded bodies. Molded bodies obtainable from the thermoplastic molding compositions according to claims 1 to 8. 344, Lisbon, FEB. 2001 Dr. Américo d ?. Silva Carvalho Agsntc 0/0. 1, 1, 2, 3, 4, 5, 6,